Triazine-ring-containing polymer and composition containing same

ABSTRACT

For example, a thin film which has a high refractive index and which it is possible to form a fine pattern can be obtained by using a composition that contains a triazine-ring-containing polymer that includes a repeating unit structure represented by formula [5].

TECHNICAL FIELD

The present invention relates to a triazine ring-containing polymer anda composition that includes the same.

BACKGROUND ART

In recent years, a need has arisen for high-performance polymericmaterials in the development of electronic devices such asliquid-crystal displays, organic electroluminescent (EL) displays, touchpanels, optical semiconductor (LED) devices, solid-state image sensors,organic thin-film solar cells, dye-sensitized solar cells and organicthin-film transistors (TFT).

The specific properties desired of such materials include: (1) heatresistance, (2) transparency, (3) high refractive index, (4) highsolubility, (5) low volume shrinkage, (6) high moisture resistance athigh temperatures, and (7) high film hardness.

The inventors earlier discovered that polymers containing recurringunits which have a triazine ring and an aromatic ring possess a highrefractive index and are able, with the polymer alone, to achieve a highheat resistance, high transparency, high refractive index, highsolubility and low volume shrinkage, thus making such polymers suitableas film-forming compositions in the fabrication of electronic devices(Patent Document 1).

Of related interest, pattern formation using transparent materials iscarried out in spacers, insulating films, protective films and the likefor liquid-crystal display elements. Many negative-workingphotosensitive compositions have hitherto been described for suchapplications.

In particular, recently, with the increased demand for high-definitionliquid-crystal displays and cell phone displays, there has arisen adesire for small patterns 10 μm or less in diameter.

Also, in touch panels, to enhance the visibility of the transparentelectrode, there is an increased need for a high refractive index layer.However, the presence of an insulating film in electrode wiring areasaffects responsiveness, and so it is necessary to remove the insulatinglayer over a width of 100 to 1,000 μm from the wiring areas.

Existing materials used in this application are inadequate in terms ofrefractive index. Moreover, it is difficult to increase the refractiveindex above 1.7 while maintaining the transparency.

Although the polymer of Patent Document 1 is able to address such needsin terms of the refractive index, there remains room for improvementwith regard to fine pattern formability.

Patent Document 2 discloses a pattern-forming composition that includesa triazine ring-containing polymer, but this polymer has a refractiveindex of less than 1.7 and is thus unsuitable for the above applicationsrequiring a higher index of refraction.

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: WO 2010/128661

Patent Document 2: JP-A 2004-156001

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

It is therefore an object of the invention to provide a triazinering-containing polymer which can form a thin film having a highrefractive index and excellent transparency and which is also capable offorming a fine pattern having a high refractive index. Another object isto provide a composition containing such a polymer.

Means for Solving the Problems

The inventors have conducted extensive investigations in order toachieve these objects. As a result, they have discovered that, by usinga triazine ring-containing polymer having carboxyl groups on aryl groupsmaking up the main chain, thin films having a high refractive index andexcellent transparency can be formed and fine patterns having a highrefractive index can also be formed.

Accordingly, the invention provides:

-   1. A triazine ring-containing polymer which includes a recurring    unit structure of formula (1) below

wherein R and R′ are each independently a hydrogen atom, an alkyl group,an alkoxy group, an aryl group or an aralkyl group; and

Ar¹ is at least one moiety selected from the group consisting ofmoieties of formulas (2) to (13)

[wherein R¹ to R⁹² are each independently a hydrogen atom, a halogenatom, a carboxyl group, a sulfo group, an alkyl group of 1 to 10 carbonatoms which may have a branched structure, or an alkoxy group of 1 to 10carbon atoms which may have a branched structure; R⁹³ and R⁹⁴ are each ahydrogen atom or an alkyl group of 1 to 10 carbon atoms which may have abranched structure; W¹ and W² are each independently a single bond,CR⁹⁵R⁹⁶ (wherein R⁹⁵ and R⁹⁶ are each independently a hydrogen atom oran alkyl group of 1 to 10 carbon atoms which may have a branchedstructure, and R⁹⁵ and R⁹⁶ may together form a ring), C═O, O, S, SO, SO₂or NR⁹⁷ (R⁹⁷ being a hydrogen atom or an alkyl group of 1 to 10 carbonatoms which may have a branched structure); and X¹ and X² are eachindependently a single bond, an alkylene group of 1 to 10 carbon atomswhich may have a branched structure, or a group of formula (14)

(wherein R⁹⁸ to R¹⁰¹ are each independently a hydrogen atom, a halogenatom, a carboxyl group, a sulfo group, an alkyl group of 1 to 10 carbonatoms which may have a branched structure, or an alkoxy group of 1 to 10carbon atoms which may have a branched structure; and Y¹ and Y² are eachindependently a single bond or an alkylene group of 1 to 10 carbon atomswhich may have a branched structure);

with the proviso that formulas (2) to (13) all have at least onecarboxyl group on one aromatic ring therein];

-   2. The triazine ring-containing polymer of 1 above which further    includes a recurring unit structure of formula (1′) below

(wherein R and R′ are each independently a hydrogen atom, an alkylgroup, an alkoxy group, an aryl group or an aralkyl group; and

Ar² is at least one moiety selected from the group consisting ofmoieties of formulas (2′) to (13′)

[wherein R^(1′) to R^(92′) are each independently a hydrogen atom, ahalogen atom, a sulfo group, an alkyl group of 1 to 10 carbon atomswhich may have a branched structure, or an alkoxy group of 1 to 10carbon atoms which may have a branched structure; R⁹³ and R⁹⁴ are each ahydrogen atom or an alkyl group of 1 to 10 carbon atoms which may have abranched structure; W¹ and W² are each independently a single bond,CR⁹⁵R⁹⁶ (wherein R⁹⁵ and R⁹⁶ are each independently a hydrogen atom oran alkyl group of 1 to 10 carbon atoms which may have a branchedstructure, and R⁹⁵ and R⁹⁶ may together form a ring), C═O, O, S, SO,SO₂, or NR⁹⁷ (R⁹⁷ being a hydrogen atom or an alkyl group of 1 to 10carbon atoms which may have a branched structure); and X^(1′) and X^(2′)are each independently a single bond, an alkylene group of 1 to 10carbon atoms which may have a branched structure, or a group of formula(14′)

(wherein R^(98′) to R^(101′) are each independently a hydrogen atom, ahalogen atom, a sulfo group, an alkyl group of 1 to 10 carbon atomswhich may have a branched structure, or an alkoxy group of 1 to 10carbon atoms which may have a branched structure; and Y¹ and Y² are eachindependently a single bond or an alkylene group of 1 to 10 carbon atomswhich may have a branched structure)];

-   3. The triazine ring-containing polymer of 1 above, wherein Ar¹ has    formula (15)

-   4. The triazine ring-containing polymer of 3 above, wherein Ar¹ has    formula (16)

-   5. The triazine ring-containing polymer of 2 above, wherein Ar² has    formula (17)

-   6. The triazine ring-containing polymer of any of 1 to 5 above,    wherein the polymer has at least one triazine ring end, and at least    a portion of the triazine ring ends are capped with an arylamino    group that may be substituted with an alkyl, alkoxy, aryl or aralkyl    group;-   7. The triazine ring-containing polymer of 6 above, wherein the    arylamino group has the alkyl, alkoxy, aryl or aralkyl group at at    least one ortho position to the amino group thereon;-   8. The triazine ring-containing polymer of 7 above, wherein the    arylamino group has the alkyl, alkoxy, aryl or aralkyl group at both    ortho positions to the amino group thereon;-   9. The triazine ring-containing polymer of 8 above, wherein the    arylamino group has formula (18)

-   10. A triazine polymer-containing composition comprising the    triazine ring-containing polymer of any of 1 to 9 above and an    organic solvent;-   11. The triazine polymer-containing composition of 10 above which    further comprises a crosslinking agent;-   12. The triazine polymer-containing composition of 11 above, wherein    the crosslinking agent is a poly(meth)acrylic compound;-   13. The triazine polymer-containing composition of 11 or 12 above    for use in forming a cured film or in patterning;-   14. A cured film obtained by curing the triazine polymer-containing    composition of any of 11 to 13 above;-   15. A pattern produced from the triazine polymer-containing    composition of 11 or 12 above;-   16. An electronic device comprising a substrate and the cured film    of 14 above formed on the substrate;-   17. An optical member comprising a substrate and the cured film of    14 above formed on the substrate; and-   18. An electronic device comprising a substrate and the pattern of    15 above formed on the substrate.

Advantageous Effects of the Invention

This invention enables a thin film having a high refractive index andexcellent transparency to be formed, and also enables a fine pattern tobe formed by masking, light exposure and curing of the film, followedby, for example, alkali development.

Cured films and fine patterns produced from the inventive compositionare able to exhibit the properties of high heat resistance, highrefractive index and low volume shrinkage owing to the crosslinkedtriazine ring-containing polymer. Hence, they can be advantageously usedin the fields of electronic devices and optical materials as, forexample, components in the fabrication of liquid-crystal displays,organic electroluminescent (EL) displays, touch panels,photosemiconductor (LED) devices, solid-state image sensors, organicthin-film solar cells, dye-sensitized solar cells, organic thin-filmtransistors (TFTs), lenses, prisms, cameras, binoculars, microscopes,semiconductor steppers and the like.

In particular, because cured films and fine patterns produced from theinventive composition have a high transparency and also a high index ofrefraction, the visibility of transparent conductive films made ofindium tin oxide (ITO), silver nanowires or the like can be improved anddeterioration of the transparent conductive film can be minimized.

Moreover, high refractive index patterns produced from the inventivecomposition can be advantageously used in applications for which highrefractive index patterns are required, such as to prevent thetransparent electrodes in the above touch panels from being visuallyapparent, light extraction applications for organic EL displays, andblack matrix applications.

BRIEF DESCRIPTION OF THE DIAGRAMS

FIG. 1 shows the ¹H-NMR spectrum for Polymeric Compound [5] obtained inWorking Example 1-1.

FIG. 2 shows the ¹H-NMR spectrum for Polymeric Compound [6] obtained inWorking Example 1-2.

EMBODIMENT FOR CARRYING OUT THE INVENTION

The invention is described more fully below.

The triazine ring-containing polymer of this invention includes arecurring unit structure of formula (1) below.

In the formula, R and R′ are each independently a hydrogen atom, analkyl group, an alkoxy group, an aryl group or an aralkyl group. Fromthe standpoint of further increasing the refractive index, both arepreferably hydrogen atoms.

In the invention, the number of carbon atoms on the alkyl group,although not particularly limited, is preferably from 1 to 20. Tofurther increase the heat resistance of the polymer, the number ofcarbon atoms is more preferably from 1 to 10, and even more preferablyfrom 1 to 3. The structure may be acyclic, branched or cyclic.

Illustrative examples of the alkyl group include methyl, ethyl,n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl,cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, n-pentyl,1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl,1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl,1-ethyl-n-propyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl,3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl,1-ethylcyclopropyl, 2-ethylcyclopropyl, n-hexyl, 1-methyl-n-pentyl,2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl,1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl,2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl,1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl,1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl,1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methylcyclopentyl,2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl,2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl,1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl,2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl,2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl,1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl,2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl,2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl and2-ethyl-3-methylcyclopropyl groups.

The number of carbon atoms on the alkoxy group, although notparticularly limited, is preferably from 1 to 20. To further increasethe heat resistance of the polymer, the number of carbon atoms is morepreferably from 1 to 10, and even more preferably from 1 to 3. Thestructure of the alkyl moiety thereon may be acyclic, branched orcyclic.

Illustrative examples of the alkoxy group include methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy,n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy,1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy,1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy,2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy,1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy,2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy,1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy,1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy and1-ethyl-2-methyl-n-propoxy groups.

The number of carbon atoms on the aryl group, although not particularlylimited, is preferably from 6 to 40. To further increase the heatresistance of the polymer, the number of carbon atoms is more preferablyfrom 6 to 16, and even more preferably from 6 to 13.

Illustrative examples of the aryl group include phenyl, o-chlorophenyl,m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl,o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl,α-naphthyl, β-naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl,1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl,3-phenanthryl, 4-phenanthryl and 9-phenanthryl groups.

The number of carbon atoms on the aralkyl group, although notparticularly limited, is preferably from 7 to 20. The alkyl moietythereon may be acyclic, branched or cyclic.

Illustrative examples include benzyl, p-methylphenylmethyl,m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl,p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl,4-isobutylphenylmethyl and α-naphthylmethyl groups.

Ar¹ represents at least one moiety selected from the group consisting ofmoieties of formulas (2) to (13).

R¹ to R⁹² above each independently represent a hydrogen atom, a halogenatom, a carboxyl group, a sulfo group, an alkyl group of 1 to 10 carbonatoms which may have a branched structure, or an alkoxy group of 1 to 10carbon atoms which may have a branched structure; R⁹³ and R⁹⁴ eachrepresent a hydrogen atom or an alkyl group of 1 to 10 carbon atomswhich may have a branched structure; and W¹ and W² each independentlyrepresent a single bond, CR⁹⁵R⁹⁶ (wherein R⁹⁵ and R⁹⁶ are eachindependently a hydrogen atom or an alkyl group of 1 to 10 carbon atomswhich may have a branched structure, and R⁹⁵ and R⁹⁶ may together form aring), C═O, O, S, SO, SO₂, or NR⁹⁷ (wherein R⁹⁷ is a hydrogen atom or analkyl group of 1 to 10 carbon atoms which may have a branchedstructure).

Examples of the halogen atom include fluorine, chlorine, bromine andiodine atoms.

The alkyl groups and alkoxy groups are exemplified in the same way asabove.

X¹ and X² each independently represent a single bond, an alkylene groupof 1 to 10 carbon atoms which may have a branched structure, or a groupof formula (14).

R⁹⁸ to R¹⁰¹ above each independently represent a hydrogen atom, ahalogen atom, a carboxyl group, a sulfo group, an alkyl group of 1 to 10carbon atoms which may have a branched structure, or an alkoxy group of1 to 10 carbon atoms which may have a branched structure; and Y¹ and Y²each independently represent a single bond or an alkylene group of 1 to10 carbon atoms which may have a branched structure. These halogenatoms, alkyl groups and alkoxy groups are exemplified in the same way asabove.

The alkylene group of 1 to 10 carbon atoms which may have a branchedstructure is exemplified by methylene, ethylene, propylene,trimethylene, tetramethylene and pentamethylene groups.

In this invention, to increase the solubility of the resulting thin filmor cured film in an alkali developing solution, the recurring unitstructure of formula (1) has, in Ar¹, at least one carboxyl group on anaromatic ring.

What is meant by the recurring unit structure of formula (1) having atleast one carboxyl group on an aromatic ring of Ar¹ is that formulas (2)to (13) all have at least one carboxyl group on at least one aromaticring thereof. Specifically, this means that at least one of R¹ to R⁴ informula (2) is a carboxyl group, at least one of R⁵ to R¹⁰ in formula(3) is a carboxyl group, at least one of R¹¹ to R¹⁵ in formula (4) is acarboxyl group, at least one of R¹⁶ to R²³ in formula (5) is a carboxylgroup, at least one of R²⁴ to R³¹ in formula (6) is a carboxyl group, atleast one of R³² to R³⁷ in formula (7) is a carboxyl group, at least oneof R³⁸ to R⁴⁴ in formula (8) is a carboxyl group, at least one of R⁴⁵ toR⁵⁶ in formula (9) is a carboxyl group, at least one of R⁵⁷ to R⁶⁸ informula (10) is a carboxyl group, at least one of R⁶⁹ to R⁷⁶ in formula(11) is a carboxyl group (when X¹ and/or X² has formula (14), at leastone of R⁶⁹ to R⁷⁶ and R⁹⁸ to R¹⁰¹ is a carboxyl group), at least one ofR⁷⁷ to R⁸⁴ in formula (12) is a carboxyl group, and at least one of R⁸⁵to R⁹² in formula (13) is a carboxyl group.

Although the number of carboxyl groups is not particularly limited,taking into account the balance between developability in an alkalideveloping solution and solubility in an organic solvent, it ispreferable for there to be one carboxyl group in each of the moietiesrepresented by formulas (2) to (13).

In particular, Ar¹ is preferably at least one moiety of formula (2) andformulas (5) to (13), and more preferably at least one moiety offormulas (2), (5), (7), (8) and (11) to (13). Specific examples of arylmoieties of formulas (2) to (13) include, but are not limited to, thosehaving the formulas shown below.

Of these, aryl moieties of the following formulas are more preferredbecause a polymer having a higher refractive index can be obtained.

In addition, taking into account the balance between developability inan alkali developing solution and solubility in an organic solvent, Ar¹is preferably a group of formula (15), and more preferably the group offormula (16).

The triazine ring-containing polymer of the invention may be oneconsisting solely of recurring units of formula (1), although itpreferably includes, together with the recurring unit structure offormula (1), recurring units represented by formula (1′) that areobtained using a diamine having no carboxyl groups.

By having the triazine ring-containing polymer of the invention be sucha copolymer in which two different types of diamines are used together,the solubility of the polymer in very safe solvents such as resistsolvents can be further increased.

In formula (1′), R and R′ are as defined above, and Ar² represents atleast one moiety selected from the group consisting of moieties offormulas (2′) to (13′) below.

Here, R^(1′) to R^(92′) each independently represent a hydrogen atom, ahalogen atom, a sulfo group, an alkyl group of 1 to 10 carbons which mayhave a branched structure, or an alkoxy group of 1 to 10 carbons whichmay have a branched structure; R⁹³ and R⁹⁴ each represent a hydrogenatom or an alkyl group of 1 to 10 carbons which may have a branchedstructure; and W¹ and W² each independently represent a single bond,CR⁹⁵R⁹⁶ (wherein R⁹⁵ and R⁹⁶ arc each independently a hydrogen atom oran alkyl group of 1 to 10 carbons which may have a branched structure,and R⁹⁵ and R⁹⁶ may together form a ring), C═O, O, S, SO, SO₂, or NR⁹⁷(wherein R⁹⁷ is a hydrogen atom or an alkyl group of 1 to 10 carbonswhich may have a branched structure). These halogen atoms, alkyl groupsand alkoxy groups are exemplified in the same way as above.

Also, X^(1′) and X^(2′) each independently represent a single bond, analkylene group of 1 to 10 carbon atoms which may have a branchedstructure, or a group of formula (14′).

Here, R^(98′) to R^(101′) each independently represent a hydrogen atom,a halogen atom, a sulfo group, an alkyl group of 1 to 10 carbon atomswhich may have a branched structure, or an alkoxy group of 1 to 10carbon atoms which may have a branched structure; and Y¹ and Y² are asdefined above. These halogen atoms, alkyl groups and alkoxy groups areexemplified in the same way as above.

In particular, Ar² is preferably at least one moiety of formula (2′) andformulas (5′) to (13′), and more preferably at least one moiety offormulas (2′), (5′), (7′), (8′) and (11′) to (13′). Specific examples ofaryl moieties of formulas (2′) to (13′) include, but are not limited to,those having the formulas shown below.

Of these, aryl moieties of the following formulas are more preferredbecause a polymer having a higher refractive index can be obtained.

In particular, to further increase the solubility of the triazinering-containing polymer in very safe solvents such as resist solvents,Ar² is preferably the m-phenylene group shown in formula (17).

In cases where the polymer is such a copolymer, the ratio of the contentof recurring units of formula (1) to the content of recurring units offormula (1′) is not particularly limited. However, taking into accountthe balance between the alkali solubility and the solubility in organicsolvents, this ratio, expressed as a molar ratio, is preferably fromabout 50:50 to about 99:1, more preferably from 60:40 to 90:10, and evenmore preferably from 65:35 to 80:20.

Moreover, in cases where the polymer is a copolymer, in addition to therecurring units of formulas (1) and (1′) above, recurring units offormula (1″) are also included in the polymer obtained.

In the present invention, examples of especially preferred triazinering-containing polymers include those of formulas (19) to (22) and(19′) to (22′) below:

(wherein R, R′, R¹ to R⁴ and R^(1′) to R^(4′) are as defined above,although only one of R¹ to R⁴ is a carboxyl group);

(wherein R, R′ and R^(1′) to R^(4′) are as defined above, and R¹, R² andR⁴ are groups other than carboxyl groups from among the above-mentionedgroups);

(wherein R^(1′) to R^(4′) are as defined above, and R¹, R² and R⁴ aregroups other than carboxyl groups from among the above-mentionedgroups);

(wherein R, R′ and R¹ to R⁴ are as defined above, although only one ofR¹ to R⁴ is a carboxyl group);

(wherein R and R′ are as defined above, and R¹, R² and R⁴ are groupsother than carboxyl groups from among the above-mentioned groups);

(wherein R¹, R² and R⁴ are groups other than carboxyl groups from amongthe above-mentioned groups); and

The polymer of the invention has a weight-average molecular weightwhich, although not particularly limited, is preferably between 500 and500,000, and more preferably between 500 and 100,000. To further enhancethe heat resistance and lower the shrinkage ratio, the Mw is preferablyat least 2,000. To further increase the solubility and lower theviscosity of the resulting solution, the weight-average molecular weightis preferably 50,000 or less, more preferably 30,000 or less, and evenmore preferably 10,000 or less.

The weight-average molecular weight in this invention is the averagemolecular weight measured by gel permeation chromatography (GPC) againsta polystyrene standard.

The triazine ring-containing polymer (hyperbranched polymer) of theinvention may be prepared by the method disclosed in above-cited PatentDocument 1.

For example, as shown in Scheme 1 below, a triazine ring-containingpolymer (22) can be obtained by reacting a triazine compound (23), acarboxyl group-containing aryldiamino compound (24) and a carboxylgroup-lacking aryldiamino compound (25) in a suitable organic solvent.

In the above formulas, each X independently represents a halogen atom.

In the above reaction, the diamino compounds (24) and (25) may becharged in any ratio so long as the target polymer can be obtained,although the combined amount of diamino compounds (24) and (25) perequivalent of the triazine compound (23) is preferably from 0.01 to 10equivalents, and more preferably from 1 to 5 equivalents. The chargingratio of the carboxyl group-containing aryldiamino compound (24) and thecarboxyl group-lacking aryldiamino compound (25), expressed as the molarratio “diamino compound (24) : diamino compound (25)”, is preferablyfrom about 50:50 to about 99:1, more preferably from 60:40 to 90:10, andeven more preferably from 65:35 to 80:20.

Diamino compounds (24) and (25) may be added neat or may be added as asolution obtained by dissolution in an organic solvent, although thelatter approach is preferred for reasons having to do with the ease ofthe operations and the controllability of the reaction.

The reaction temperature should be suitably set in the range from themelting point to the boiling point of the solvent used, although thetemperature is preferably from about −30° C. to about 150° C., and morepreferably from −10° C. to 100° C.

Various solvents that are commonly used in this type of reaction may beused as the organic solvent. Illustrative examples includetetrahydrofuran, dioxane, dimethylsulfoxide, amide solvents such asN,N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea,hexamethylphosphoramide, N,N-dimethylacetamide, N-methyl-2-piperidone,N,N-dimethylethyleneurea, N,N,N′,N′-tetramethylmalonamide,N-methylcaprolactam, N-acetylpyrrolidine, N,N-diethylacetamide,N-ethyl-2-pyrrolidone, N,N-dimethylpropionamide,N,N-dimethylisobutyramide, N-methylformamide and N,N′-dimethylpropyleneurea; and mixed solvents thereof.

Of these, N,N-dimethylformamide, dimethylsulfoxide,N-methyl-2-pyrrolidone, N,N-dimethylacetamide and mixed solvents thereofare preferred. N,N-dimethylacetamide and N-methyl-2-pyrrolidone areespecially preferred.

In the Scheme 1 reactions above, various bases which are commonly usedduring or after polymerization may be added.

Illustrative examples of such bases include potassium carbonate,potassium hydroxide, sodium carbonate, sodium hydroxide, sodiumbicarbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithiumhydroxide, lithium oxide, potassium acetate, magnesium oxide, calciumoxide, barium hydroxide, trilithium phosphate, trisodium phosphate,tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia,n-propylamine, trimethylamine, triethylamine, diisopropylamine,diisopropylethylamine, N-methylpiperidine,2,2,6,6-tetramethyl-N-methylpiperidine, pyridine,4-dimethylaminopyridine and N-methylmorpholine.

The amount of base added per equivalent of the triazine compound (23) ispreferably from 1 to 100 equivalents, and more preferably from 1 to 10equivalents. These bases may be used in the form of an aqueous solution.

It is preferable for there to be no residual starting ingredients withinthe resulting polymer, although the residual presence of some startingmaterial is acceptable so long as this does not detract from theadvantageous effects of the invention.

Following reaction completion, the product can be easily purified by asuitable technique such as re-precipitation.

It is preferable for the triazine ring-containing polymer of theinvention to have at least one triazine ring end, and for at least aportion of the triazine ring ends to be capped with an arylamino groupthat may be substituted with an alkyl, alkoxy, aryl or aralkyl group.

The aryl group on the arylamino group is exemplified in the same way asdescribed above, with a phenyl group being preferred.

In particular, from the standpoint of ensuring the solubility of thetriazine ring-containing polymer in very safe solvents such as resistsolvents, the arylamino group is more preferably substituted with analkyl, alkoxy, aryl or aralkyl group, even more preferably has an alkyl,alkoxy, aryl or aralkyl group at at least one ortho position to theamino group, and still more preferably has an alkyl, alkoxy, aryl oraralkyl group at both ortho positions to the amino group.

The substituent on the arylamino group is preferably an alkyl group of 1to 20 carbon atoms, more preferably an alkyl group of 1 to 10 carbonatoms, and even more preferably an alkyl group of 1 to 5 carbon atoms.

These alkyl, alkoxy, aryl and aralkyl groups are exemplified in the sameway as described above.

For the above reasons, the arylamino group is preferably one having analkyl group of 1 to 20 carbon atoms at at least one ortho position tothis amino group, more preferably one having an alkyl group of 1 to 5carbon atoms at both ortho position, and most preferably the phenylaminogroup having methyl groups at both ortho positions shown in formula (18)below.

A known method may be used as the end-capping method. For example, thetriazine ring-containing polymer (22) obtained by the above method maybe treated with, as an end-capping agent that provides an end-cappinggroup, the above-described arylamine compound having a givensubstituent.

In this case, the amount of end-capping agent used per equivalent ofhalogen atoms from the excess triazine compound not utilized in thepolymerization reaction is preferably from about 0.05 to about 10equivalents, more preferably from 0.1 to 5 equivalents, and even morepreferably from 0.5 to 2 equivalents.

The reaction solvent and temperature are exemplified by the sameconditions as mentioned above for Scheme 1, and the end-capping agentmay be charged at the same time as the aryldiamine compound.

End-capping with two or more types of groups may be carried out by usingan arylamine compound without any substituents together with theabove-described arylamine compound having a given substituent.

The triazine ring-containing polymer of the invention can be suitablyused, together with a crosslinking agent, as a film-forming compositionor a patterning composition.

The crosslinking agent is not particularly limited, provided it is acompound having a substituent that can react with the triazinering-containing polymer.

Such compounds are exemplified by melamine compounds having acrosslink-forming substituent such as a methylol group or amethoxymethyl group, substituted urea compounds, compounds having acrosslink-forming substituent such as an epoxy group or an oxetanegroup, blocked isocyanate-containing compounds, acidanhydride-containing compounds, compounds having a (meth)acrylic group,and phenoplast compounds. From the standpoint of heat resistance andstorage stability, compounds having an epoxy group, a blocked isocyanategroup or a (meth)acrylic group are preferred. Compounds having a blockedisocyanate group, and polyepoxy compounds and/or poly(meth)acryliccompounds which provide a photocurable composition even without the useof an initiator are especially preferred.

When used for polymer end group treatment, these compounds should haveat least one crosslink-forming substituent. When used for crosslinkingtreatment between polymers, they must have at least twocrosslink-forming substituents.

The polyepoxy compound is not particularly limited, provided it has atleast two epoxy groups on the molecule.

Illustrative examples include tris(2,3-epoxypropyl) isocyanurate,1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane,glycerol triglycidyl ether, diethylene glycol diglycidyl ether,2,6-diglycidylphenyl glycidyl ether,1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane,1,2-cyclohexanedicarboxylic acid diglycidyl ester,4,4′-methylenebis(N,N-diglycidylaniline),3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate,trimethylolethane triglycidyl ether, bisphenol A diglycidyl ether andpentaerythritol polyglycidyl ether.

Examples of commercial products that may be used include epoxy resinshaving at least two epoxy groups, such as YH-434 and YH-434L (from TohtoKasei Co., Ltd.); epoxy resins having a cyclohexene oxide structure,such as Epolead GT-401, GT-403, GT-301 and GT-302, and also Celloxide2021 and Celloxide 3000 (all from Daicel Chemical Industries, Ltd.);bisphenol A-type epoxy resins such as Epikote (now “jER”) 1001, 1002,1003, 1004, 1007, 1009, 1010 and 828 (all from Japan Epoxy Resin Co.,Ltd.); bisphenol F-type epoxy resins such as Epikote (now “jER”) 807(Japan Epoxy Resin Co., Ltd.); phenol-novolak type epoxy resins such asEpikote (now “jER”) 152 and 154 (Japan Epoxy Resin Co., Ltd.), and EPPN201 and 202 (Nippon Kayaku Co., Ltd.); cresol-novolak type epoxy resinssuch as EOCN-102, 103S, 104S, 1020, 1025 and 1027 (Nippon Kayaku Co.,Ltd.), and Epikote (now “jER”) 180S75 (Japan Epoxy Resin Co., Ltd.);alicyclic epoxy resins such as Denacol EX-252 (Nagase ChemteXCorporation), CY175, CY177 and CY179 (Ciba-Geigy AG), Araldite CY-182,CY-192 and CY-184 (Ciba-Geigy AG), Epiclon 200 and 400 (DICCorporation), Epikote (now “jER”) 871 and 872 (Japan Epoxy Resin Co.,Ltd.), and ED-5661 and ED-5662 (Celanese Coating KK); and aliphaticpolyglycidyl ethers such as Denacol EX-611, EX-612, EX-614, EX-622,EX-411, EX-512, EX-522, EX-421, EX-313, EX-314 and EX-321 (NagaseChemteX. Corporation).

The poly(meth)acrylic compounds are not particularly limited, providedthey have two or more (meth)acrylic groups per molecule.

Illustrative examples include ethylene glycol diacrylate, ethyleneglycol dimethacrylate, polyethylene glycol diacrylate, polyethyleneglycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylatedbisphenol A dimethacrylate, ethoxylated trimethylolpropane triacrylate,ethoxylated trimethylolpropane trimethacrylate, ethoxylated glyceroltriacrylate, ethoxylated glycerol trimethacrylate, ethoxylatedpentaerythritol tetraacrylate, ethoxylated pentaerythritoltetramethacrylate, ethoxylated dipentaerythritol hexaacrylate,polyglycerol monoethylene oxide polyacrylate, polyglycerol polyethyleneglycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritolhexamethacrylate, neopentyl glycol diacrylate, neopentyl glycoldimethacrylate, pentaerythritol triacrylate, pentaerythritoltrimethacrylate, trimethylolpropane triacrylate, trimethylolpropanetrimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecanedimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanedioldimethacrylate and polybasic acid-modified acrylic oligomers.

The poly(meth)acrylic compound may be acquired as a commercial product,illustrative examples of which include NK Ester A-200, A-400, A-600,A-1000, A-9300 (tris(2-acryloyloxyethyl) isocyanurate), A-9300-1CL,A-TMPT, UA-53H, 1G, 2G, 3G, 4G, 9G, 14G, 23G, ABE-300, A-BPE-4, A-BPE-6,A-BPE-10, A-BPE-20, A-BPE-30, BPE-80N, BPE-100N, BPE-200, BPE-500,BPE-900, BPE-1300N, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO,A-TMPT-9EO, AT-20E, ATM-4E, ATM-35E, A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT,DCP, NPG, HD-N, A-DPH-48E and A-DPH-96E, and also NK Oligo U-15HA and NKPolymer Vanaresin GH-1203 (all from Shin-Nakamura Chemical Co., Ltd.);KAYARAD® DPHA, NPGDA, PET30, DPEA-12, PEG400DA, THE-330, RP-1040 andDN-0075 (all from Nippon Kayaku Co., Ltd.); Aronix® M-210, M-303, M-305,M-306, M-309, M-310,M-313, M-315, M-321, M-350, M-360, M-400, M-402,M-403, M-404, M-405, M-406, M-408, M-450, M-452 and M-460 (from ToagoseiCo., Ltd.); and DPGDA, HDDA, TPGDA, HPNDA, PETIA, PETRA, TMPTA, TMPEOTA,EBECRYL 11, 40, 135, 140, 145, 150, 180, 1142, 204, 205, 210, 215, 220,230, 244, 245, 265, 270, 280/15IB, 284, 294/25HD, 303, 436, 438, 446,450, 524, 525, 600, 605, 645, 648, 767, 770, 800, 810, 811, 812, 846,851, 852, 853, 860, 884, 885, 1259, 1290, 1606, 1830, 1870, 3500, 3603,3608, 3700, 3701, 3702, 3703, 3708, 4820, 4858, 5129, 6040, 8210, 8454,8301R, 8307, 8311, 8402, 8405, 8411, 8465, 8701, 8800, 8804, 8807, 9270,9227EA and 936, KRM8200, 8200AE, 7735, 8296, 08452, 8904, 8528 and 8912,OTA480, IRR214-K, 616, 679, 742 and 793, and PEG400DA-D (ACA) Z200M,Z230AA, Z250, Z251, Z300, Z320 and Z254F (all from Daicel-Allnex Ltd.).

The above polybasic acid-modified acrylic oligomers are also availableas commercial products, illustrative examples of which include AronixM-510 and 520 (Toagosei Co., Ltd.).

The acid anhydride compounds are not particularly limited, provided theyare carboxylic acid anhydrides obtained by the dehydration/condensationof two molecules of carboxylic acid. Illustrative examples include thosehaving one acid anhydride group per molecule, such as phthalicanhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride,nadic anhydride, methyl nadic anhydride, maleic anhydride, succinicanhydride, octyl succinic anhydride and dodecenyl succinic anhydride;and those having two acid anhydride groups per molecule, such as1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic anhydride,3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride,bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride,5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylicanhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride,2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride and1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride.

The blocked isocyanate-containing compounds are not particularlylimited, provided they are compounds having at least two blockedisocyanate groups per molecule, i.e., isocyanate groups (—NCO) that havebeen blocked with suitable protecting groups, and in which, uponexposure of the compound to an elevated temperature during heat curing,the protecting groups (blocking moieties) are removed by thermaldissociation and the isocyanate groups that form as a result inducecrosslinking reactions with the resin. Such compounds are exemplified bycompounds having at least two groups of the following formula (whichgroups may be the same or may each differ) per molecule.

In the formula, R_(b) is an organic group on the blocking moiety.

Such a compound can be obtained by, for example, reacting a suitableblocking agent with a compound having two or more isocyanate groups permolecule.

Examples of compounds having two or more isocyanate groups per moleculeinclude polyisocyanates such as isophorone diisocyanate,1,6-hexamethylene diisocyanate, methylenebis(4-cyclohexyl isocyanate)and trimethylhexamethylene diisocyanate, and also dimers and trimersthereof, as well as the reaction products of these with diols, triols,diamines or triamines.

Examples of the blocking agent include alcohols such as methanol,ethanol, isopropanol, n-butanol, 2-ethoxyhexanol,2-N,N-dimethylaminoethanol, 2-ethoxyethanol and cyclohexanol; phenolssuch as phenol, o-nitrophenol, p-chlorophenol, and o-, m- and p-cresol;lactams such as E-caprolactam; oximes such as acetone oxime, methylethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime,acetophenone oxime and benzophenone oxime; pyrazoles such as pyrazole,3,5-dimethylpyrazole and 3-methylpyrazole; and thiols such asdodecanethiol and benzenethiol.

Compounds containing blocked isocyanate groups may also be acquired ascommercial products, examples of which include Takenate® B-830, B-815N,B-842N, B-870N, B-874N, B-882N, B-7005, B7030, B-7075 and B-5010 (allfrom Mitsui Chemicals Polyurethanes, Inc.); Duranate® 17B-60PX,TPA-B80E, MF-B60X, MF-K60X and E402-B80T (all from Asahi Kasei ChemicalsCorporation); KarenzMOI-BM™ (Showa Denko KK); and Trixene BI® 7950,7951, 7960, 7961, 7982, 7990, 7991 and 7992 (all from BaxendenChemical).

The aminoplast compounds are not particularly limited, provided they arecompounds which have at least two methoxymethylene groups per molecule.Examples include the following melamine compounds: compounds of theCymel® series, such as hexamethoxymethylmelamine (Cymel® 303),tetrabutoxymethylglycoluril (Cymel® 1170) andtetramethoxymethylbenzoguanamine (Cymel® 1123) (all from Nihon CytecIndustries, Inc.); and compounds of the Nikalac® series, including themethylated melamine resins Nikalac® MW-30HM, MW-390, MW-100LM andMX-750LM, and the methylated urea resins Nikalac® MX-270, MX-280 andMX-290 (all from Sanwa Chemical Co., Ltd.).

The oxetane compounds are not particularly limited, provided they arecompounds which have at least two oxetanyl groups per molecule. Examplesinclude the oxetanyl group-containing compounds OXT-221, OX-SQ-H andOX-SC (from Toagosei Co., Ltd.).

Phenoplast compounds are compounds which have at least twohydroxymethylene groups per molecule. Upon exposure to an elevatedtemperature during heat curing, crosslinking reactions proceed by way ofdehydration/condensation reactions with the polymer of the invention.

Examples of phenoplast compounds include2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol,bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane,bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane,2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane,bis(3-formyl-4-hydroxyphenyl)methane,bis(4-hydroxy-2,5-dimethylphenyl)formylmethane andα,α-bis(4-hydroxy-2,5-dimethylphenyl)-4-formyltoluene.

The phenoplast compound may also be acquired as a commercial product,illustrative examples of which include 26DMPC, 46DMOC, DM-BIPC-F,DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF and BI25X-TPA (all from AsahiOrganic Chemicals Industry Co., Ltd.).

Of these, both in terms of being able to suppress a decline in therefractive index due to inclusion of a crosslinking agent and also rapidprogress of the curing reaction, poly(meth)acrylic compounds arepreferred. In particular, owing to their excellent compatibility withtriazine ring-containing polymers, poly(meth)acrylic compounds havingthe isocyanuric acid skeleton shown below are more preferred.

Poly(meth)acrylic compounds having such skeletons are exemplified by NKEster A-9300 and A-9300-1CL (both available from Shin-Nakamura ChemicalCo., Ltd.).

Here, R¹¹¹ to R¹¹³ are each independently a monovalent organic grouphaving at least one (meth)acrylic group on the end.

To further enhance the rate of cure and also increase the solventresistance, acid resistance and alkali resistance of the resulting curedfilm, it is advantageous to use a poly(meth)acrylic compound which at25° C. is a liquid and has a viscosity of 5,000 mPa·s or less,preferably from 1 to 3,000 mPa·s, more preferably from 1 to 1,000 mPa·s,and even more preferably from 1 to 500 mPa·s (referred to below as a“low-viscosity crosslinking agent”), either singly or as a combinationof two or more thereof, or in combination with the above-describedpoly(meth)acrylic compound having an isocyanuric acid skeleton.

Such a low-viscosity crosslinking agent too may be acquired as acommercial product. Examples include, of the above-mentionedpoly(meth)acrylic compounds, crosslinking agents in which the chainlengths between (meth)acrylic groups are relatively long, such as NKEster A-GLY-3E (85 mPa·s at 25° C.), A-GLY-9E (95 mPa·s at 25° C.),A-GLY-20E (200 mPa·s at 25° C.), A-TMPT-3EO (60 mPa·s at 25° C.),A-TMPT-9EO, ATM-4E (150 mPa·s at 25° C.) and ATM-35E (350 mPa·s at 25°C.) (all from Shin-Nakamura Chemical Co., Ltd.).

In addition, to enhance the alkali resistance of the resulting curedfilm, it is preferable to use a combination of at least one of NK EsterA-GLY-20E (Shin-Nakamura Chemical Co., Ltd.) and NK Ester ATM-35E(Shin-Nakamura Chemical Co., Ltd.) with the above-describedpoly(meth)acrylic compound having an isocyanuric acid skeleton.

Also, in cases where a thin-film made of the triazine ring-containingpolymer of the invention is laminated with a protective film such as aPET or polyolefin film and irradiated with light through the protectivefilm, oxygen inhibition does not occur in the laminated film, enablinggood curability to be achieved. Because there is a need in such cases topeel off the protective film after curing, it is preferable to use apolybasic acid-modified acrylic oligomer that provides a thin filmhaving good peelability.

The above crosslinking agent may be used singly, or two or more may beused in combination. The amount of crosslinking agent used per 100 partsby weight of the triazine ring-containing polymer is preferably from 1to 100 parts by weight. From the standpoint of solvent resistance, thelower limit is preferably 2 parts by weight, and more preferably 5 partsby weight. From the standpoint of controlling the refractive index, theupper limit is preferably 20 parts by weight, and more preferably 15parts by weight.

Initiators corresponding to the respective crosslinking agents may alsobe included in the composition of the invention. As noted above, when apolyepoxy compound and/or a poly(meth)acrylic compound are used ascrosslinking agents, photocuring proceeds even without the use of aninitiator, giving a cured film, although it is acceptable to use aninitiator in such cases.

When a polyepoxy compound is used as the crosslinking agent, a photoacidgenerator or a photobase generator may be used as the initiator.

The photoacid generator used may be one that is suitably selected fromamong known photoacid generators. For example, use may be made of oniumsalt derivatives such as diazonium salts, sulfonium salts or iodoniumsalts.

Illustrative examples include aryldiazonium salts such asphenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazoniumhexafluoroantimonate and 4-methylphenyldiazonium hexafluorophosphate;diaryliodonium salts such as diphenyliodonium hexafluoroantimonate,di(4-methylphenyl)iodonium hexafluorophosphate anddi(4-tert-butylphenyl)iodonium hexafluorophosphate; and triarylsulfoniumsalts such as triphenylsulfonium hexafluoroantimonate,tris(4-methoxyphenyl)sulfonium hexafluorophosphate,diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate,diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate,4,4′-bis(diphenylsulfonio)phenylsulfide bishexafluoroantimonate,4,4′-bis(diphenylsulfonio)phenylsulfide bishexafluorophosphate,4,4′-bis[di(β-hydroxyethoxy)phenylsulfonio]phenylsulfidebishexafluoroantimonate,4,4′-bis[di(β-hydroxyethoxy)phenylsulfonio]phenylsulfidebishexafluorophosphate,4-[4′-(benzoyl)phenylthio]phenyl-di(4-fluorophenyl)sulfoniumhexafluoroantimonate and4-[4′-(benzoyl)phenylthio]phenyl-di(4-fluorophenyl)sulfoniumhexafluorophosphate.

Commercial products may be used as these onium salts. Illustrativeexamples include San-Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L,SI-L145, SI-L150, SI-L160, SI-L110 and SI-L147 (all available fromSanshin Chemical Industry Co., Ltd.); UVI-6950, UVI-6970, UVI-6974,UVI-6990 and UVI-6992 (all available from Union Carbide); CPI-100P,CPI-100A, CPI-200K and CPI-200S (all available from San-Apro Ltd.);Adeka Optomer SP-150, SP-151, SP-170 and SP-171 (all available fromAdeka Corporation); Irgacure 261 (BASF); CI-2481, CI-2624, CI-2639 andCI-2064 (Nippon Soda Co., Ltd.); CD-1010, CD-1011 and CD-1012 (SartomerCompany); DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM-301,NAI-100, NAI-101, NAI-105, NAI-106, SI-100, SI-101, SI-105, SI-106,PI-105, NDI-105, BENZOIN TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200,DNB-101, NB-101, NB-201, BBI-101, BBI-102, BBI-103 and BBI-109 (all fromMidori Kagaku Co., Ltd.); PCI-061T, PCI-062T, PCI-020T and PCI-022T (allfrom Nippon Kayaku Co., Ltd.); and IBPF and IBCF (Sanwa Chemical Co.,Ltd.).

The photobase generator used may be one selected from among knownphotobase generators. For example, use may be made of Co-amminecomplex-type, oxime carboxylic acid ester-type, carbamic acid ester-typeand quaternary ammonium salt-type photobase generators.

Illustrative examples include 2-nitrobenzylcyclohexyl carbamate,triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime,[[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine,bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine,4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane,(4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane,N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III)tris(triphenylmethylborate),2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone,2,6-dimethyl-3,5-diacetyl-4-(2′-nitrophenyl)-1,4-dihydropyridine and2,6-dimethyl-3,5-diacetyl-4-(2′,4′-dinitrophenyl)-1,4-dihydropyridine.

A commercial product may be used as the photobase generator.Illustrative examples include TPS-OH, NBC-101 and ANC-101 (all availableunder these product names from Midori Kagaku Co., Ltd.).

In cases where a photoacid or photobase generator is used, the amountthereof is preferably in the range of 0.1 to 15 parts by weight, andmore preferably 1 to 10 parts by weight, per 100 parts by weight of thepolyepoxy compound.

Also, from 1 to 100 parts by weight of an epoxy resin curing agent maybe optionally included per 100 parts by weight of the polyepoxycompound.

In cases where a poly(meth)acrylic compound is used, a photoradicalinitiator may also be used.

A known photoradical initiator may be suitably selected and used forthis purpose. Exemplary photoradical initiators include acetophenones,benzophenones, Michler's benzoyl benzoate, amyloxime esters, oximeesters, tetramethylthiuram monosulfide and thioxanthones.

Photocleavable photoradical initiators are especially preferred.Photocleavable photoradical initiators are listed on page 159 of SaishinUV Kōka Gijutsu [Recent UV Curing Technology] (publisher, K. Takausu;published by Gijutsu Joho Kyokai K K; 1991).

Examples of commercial photoradical initiators include those availablefrom BASF under the trade names Irgacure 127, 184, 369, 379, 379EG, 651,500, 754, 819, 903, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61,OXE01 and OXE02, and the trade names Darocur 1116, 1173 and MBF; thatavailable from BASF under the trade name Lucirin TPO; that availablefrom UCB under the trade name Uvecryl P 36; and those available underthe trade names Esacure KIP150, KIP65LT, KIP100F, KT37, KT55, KT046 andKIP75/B from the Fratelli Lamberti Company.

The photoradical initiator is used in the range of preferably 0.1 to 200parts by weight, and more preferably 1 to 150 parts by weight, per 100parts by weight of the poly(meth)acrylic compound.

Any of various types of solvents may be added to the inventivecomposition and used to dissolve the triazine ring-containing polymer.

Illustrative examples of the solvent include water, toluene, p-xylene,o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycol dimethylether, propylene glycol monomethyl ether, ethylene glycol monomethylether, propylene glycol, propylene glycol mono ethyl ether, ethyleneglycol monoethyl ether, ethylene glycol monoisopropyl ether, ethyleneglycol methyl ether acetate, propylene glycol monomethyl ether acetate,ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether,propylene glycol monobutyl ether, ethylene glycol monobutyl ether,diethylene glycol diethyl ether, dipropylene glycol monomethyl ether,diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether,diethylene glycol monoethyl ether, triethylene glycol dimethyl ether,diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol,ethylene glycol, hexylene glycol, trimethylene glycol,1-methoxy-2-butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol,tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol,1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyrolactone,acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone,methyl isobutyl ketone, methyl n-butyl ketone, cyclopentanone,cyclohexanone, ethyl acetate, isopropyl acetate, n-propyl acetate,isobutyl acetate, n-butyl acetate, ethyl lactate, methanol, ethanol,isopropanol, tert-butanol, allyl alcohol, n-propanol,2-methyl-2-butanol, isobutanol, n-butanol, 2-methyl-1-butanol,1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, 1-methoxy-2-propanol,tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide,N,N-dimethylacetamide (DMAc), N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide andN-cyclohexyl-2-pyrrolidinone. These may be used singly or two or moremay be used in combination.

The solids concentration in the composition is not particularly limited,provided it is in a range that does not adversely affect the storagestability, and may be suitably selected according to the target filmthickness. Specifically, from the standpoint of solubility and storagestability, the solids concentration is preferably from 0.1 to 50 wt %,and more preferably from 0.1 to 40 wt %.

Ingredients other than the triazine ring-containing polymer,crosslinking agent and solvent may also be included in the inventivecomposition, provided that doing so does not detract from theadvantageous effects of the invention. Examples of such otheringredients include additives such as leveling agents, surfactants,silane coupling agents, polymerization inhibitors, antioxidants,corrosion inhibitors, mold release agents, plasticizers, defoamers,thickeners, dispersants, antistatic agents, sedimentation inhibitors,pigments, dyes, ultraviolet absorbers, light stabilizers and inorganicfine particles.

Illustrative examples of surfactants include the following nonionicsurfactants: polyoxyethylene alkyl ethers such as polyoxyethylene laurylether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether andpolyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such aspolyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenylether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fattyacid esters such as sorbitan monolaurate, sorbitan monopalmitate,sorbitan monostearate, sorbitan monooleate, sorbitan trioleate andsorbitan tristearate; and polyoxyethylene sorbitan fatty acid esterssuch as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitanmonopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylenesorbitan trioleate and polyoxyethylene sorbitan tristearate; andadditionally include fluorosurfactants such as those available under thetrade names Eftop EF301, EF303 and EF352 (from Mitsubishi MaterialsElectronic Chemicals Co., Ltd. (formerly Jemco Inc.)), Megafac F171,F173, R-08, R-30, R-40, R-41, F-114, F-410, F-430, F-444, F-477, F-552,F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-561, F-562, RS-75,RS-72-K RS-76-E, RS-76NS and RS-77 (DIC Corporation), Fluorad FC430 andFC431 (Sumitomo 3M, Ltd.), AsahiGuard AG710 and Surflon S-382, SC101,SC102, SC103, SC104, SC105 and SC106 (Asahi Glass Co., Ltd.); and alsothe organosiloxane polymers KP341 (Shin-Etsu Chemical Co., Ltd.) andBYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375and BYK-378 (BYK-Chemie Japan KK).

These surfactants may be used singly, or two or more may be used incombination. The amount of surfactant used per 100 parts by weight ofthe triazine ring-containing polymer is preferably from 0.0001 to 5parts by weight, more preferably from 0.001 to 1 part by weight, andeven more preferably from 0.01 to 0.5 part by weight.

Exemplary inorganic fine particles include oxides, sulfides and nitridesof one, two or more metals selected from the group consisting ofberyllium, aluminum, silicon, titanium, vanadium, iron, copper, zinc,yttrium, zirconium, niobium, molybdenum, indium, tin, antimony,tantalum, tungsten, lead, bismuth and cerium. Oxides of these metals areespecially preferred. The inorganic fine particles may be of a singletype used alone, or two or more types may be used in combination.

Illustrative examples of metal oxides include Al₂O₃, ZnO, TiO₂, ZrO₂,Fe₂O₃, Sb₂O₅, BeO, ZnO, SnO₂, CeO₂, SiO₂ and WO₃.

It is also effective to use a plurality of metal oxides as a mixedoxide. Mixed oxides refer to two or more inorganic oxides that have beenmixed together at the fine particle production stage. Illustrativeexamples include mixed oxides of TiO₂ and ZrO₂, mixed oxides of TiO₂ andZrO₂ and SnO₂, and mixed oxides of ZrO₂ and SnO₂.

In addition, compounds of the above metals may be used. Examples of suchcompounds include ZnSb₂O₆, BaTiO₃, SrTiO₃ and SrSnO₃. Such compounds maybe used singly, two or more may be used in admixture, or such compoundsmay be used in admixture with the above oxides.

The other ingredients mentioned above may be added in any step duringpreparation of the inventive composition.

The film-forming composition of the invention may be rendered into thedesired cured film by applying the composition onto a substrate, thenoptionally heating to evaporate off the solvent, followed by heating orlight irradiation.

Any suitable method may be used for applying the composition, such asspin coating, dipping, flow coating, inkjet printing, jet dispensing,spraying, bar coating, gravure coating, slit coating, roll coating,transfer printing, brush coating, blade coating and air knife coating.

Illustrative examples of the substrate include substrates made ofsilicon, indium tin oxide (ITO)-coated glass, indium zinc oxide(IZO)-coated glass, polyethylene terephthalate (PET), plastic, glass,quartz or ceramic. Use can also be made of a flexible substrate havingpliability.

The bake temperature for evaporating off the solvent is not particularlylimited. The bake may be carried out at, for example, from 110 to 400°C.

The bake process is not particularly limited. For example, evaporationmay be effected using a hot plate or an oven, such evaporation beingcarried out under a suitable atmosphere, such as in open air, innitrogen or another inert gas, or in a vacuum.

With regard to the bake temperature and time, conditions which arecompatible with the processing steps for the target electronic deviceshould be selected. Bake conditions should be selected in such a waythat the physical values of the resulting film conform to the requiredcharacteristics of the electronic device.

The conditions in cases where light irradiation is carried out are alsonot particularly limited. For example, an irradiation energy and timewhich are suitable for the triazine ring-containing polymer andcrosslinking agent used may be employed.

In the production of a cured film by irradiating the composition withlight, it is also possible to form a fine pattern by light irradiationthrough a mask, followed by development with a developing solution.

In this case, development following light exposure may be carried out byimmersing the light-exposed resin in, for example, an organicsolvent-based developing solution or an aqueous developing solution.

Examples of organic solvent-based developing solutions include thoseprepared with PGME, PGMEA, a mixed solvent of PGME and PGMEA, NMP,γ-butyrolactone, or DMSO. Examples of aqueous developing solutionsinclude alkaline aqueous solutions of, e.g., sodium carbonate, potassiumcarbonate, sodium hydroxide, potassium hydroxide or tetramethylammoniumhydroxide.

For preparation of a negative-working patterning composition, an oxiranering-containing compound and a photocuring catalyst may additionally beincluded in the above composition.

The oxirane ring-containing compound is exemplified by those having oneor more, and preferably two or more, oxirane rings on the molecule.Illustrative examples include glycidyl ether-type epoxy resins, glycidylester-type epoxy resins, alicyclic epoxy resins, epoxy-modifiedpolybutadiene resins and oxetane compounds. These may be used singly, ortwo or more may be used in combination.

The oxirane ring-containing compound content, although not particularlylimited, may be set to from about 10 to about 400 parts by weight per100 parts by weight of the triazine ring-containing polymer.

Photocuring catalysts are exemplified by photocation generators.Illustrative examples of photocation generators include triarylsulfoniumsalts such as triphenylsulfonium hex afluorophosphate andtriphenylsulfonium hexafluoroantimonate; triarylselenium salts; anddiaryliodonium salts such as diphenyliodonium hexafluorophosphate anddiphenyliodonium hexafluoroantimonate. These may be used singly, or twoor more may be used in combination.

The photocuring catalyst content, although not particularly limited, maybe set to from about 0.1 to about 100 parts by weight per 100 parts byweight of the triazine ring-containing polymer.

The method of preparing the negative-working patterning composition isnot particularly limited; preparation may be carried out by adding theingredients in any order. Also, the above-mentioned solvent may be usedat this time.

This composition, after being applied onto a substrate by theabove-described technique, may be cured by irradiation with, e.g.,ultraviolet light at a dose of 1 to 4,000 mJ/cm². Light irradiation maybe carried out using any of various known means, such as a high-pressuremercury vapor lamp, metal halide lamp, xenon lamp, LEDs or laser light.

Where necessary, the composition may be heated at about 110 to 180° C.before and after light exposure.

Development following light exposure may be carried out by immersing theexposed resin in the above-described organic solvent-based developingsolution or aqueous developing solution.

For preparation as a positive-working patterning composition, an azidecompound may additionally be included in the above composition.

The azide compound is preferably a compound having at least one, andmore preferably at least two, 1,2-naphthoquinonediazide groups.Illustrative examples include 1,2-naphthoquinonediazidosulfonic acidderivatives such as the ester of 2,3,4-trihydroxybenzophenone and1,2-naphthquinone-2-diazido-5-sulfonic acid.

The azide compound content, although not particularly limited, may beset to about 4 to 60 parts by weight per 100 parts by weight of thetriazine ring-containing polymer.

The method of preparing the positive-working patterning composition isnot particularly limited; preparation may be carried out by adding theingredients in any order. Also, the above-mentioned solvent may be usedat this time.

This composition, after being applied onto a substrate by theabove-described technique, may be cured by the above-mentionedlight-irradiating means involving irradiation with, e.g., ultravioletlight at a dose of 1 to 2,000 mJ/cm². Here too, where necessary, thecomposition may be heated at about 110 to 180° C. before and after lightexposure.

Development following light exposure may be carried out by immersing theexposed resin in the above-mentioned organic solvent-based developingsolution or aqueous developing solution.

Various types of additives may be optionally added to the abovepatterning compositions. Illustrative examples of additives includethermocation generators such as benzyl-4-hydroxyphenylmethylsulfoniumhex afluoroantimonate, 1-naphthylmethyl-4-hydroxyphenylmethylsulfoniumhexafluoroantimonate and 4-hydroxyphenyldimethylsulfonium methylsulfate; photosensitizers such as 2,5-diethylthioxanthone, anthraceneand 9,10-ethoxyanthracene; and the additives mentioned above in thedescription of the film-forming composition.

The cured films and fine patterns of the invention obtained in the abovemanner are able to attain a high heat resistance, high refractive indexand low volume shrinkage, and therefore can be suitably utilized in thefields of electronic devices and optical materials as, for example,components in the fabrication of liquid-crystal displays, organicelectroluminescent (EL) displays, touch panels, photosemiconductor (LED)devices, solid-state image sensors, organic thin-film solar cells,dye-sensitized solar cells, organic thin-film transistors (TFTs),lenses, prisms, cameras, binoculars, microscopes, semiconductor steppersand the like.

In particular, because cured films and fine patterns produced from theinventive composition have a high transparency and also have a highrefractive index, the visibility of transparent conductive films made ofITO or silver nanowires can be improved and the deterioration oftransparent conductive films can be inhibited.

The transparent conductive film is preferably an ITO film, an IZO film,or a transparent conductive film having electrically conductivenanostructures such as metal nanoparticles, metal nanowires or metalnanomeshes. A transparent conductive film having electrically conductivenanostructures is more preferred. The metal making up the conductivenanostructures is not particularly limited. Examples include silver,gold, copper, nickel, platinum, cobalt, iron, zinc, ruthenium, rhodium,palladium, cadmium, osmium, iridium, and alloys thereof. That is, atransparent conductive film having, for example, silver nanoparticles,silver nanowires, silver nanomeshes, gold nanoparticles, gold nanowires,gold nanomeshes, copper nanoparticles, copper nanowires or coppernanomeshes is preferred. A transparent conductive film having silvernanowires is especially preferred.

Moreover, high refractive index patterns produced from the inventivecomposition can be advantageously used in applications for which highrefractive index patterns are desired, such as to prevent thetransparent electrodes in the above touch panels and the like from beingvisually apparent, organic EL display light extraction applications, andblack matrix applications.

EXAMPLES

Working Examples and Comparative Examples are given below to moreconcretely illustrate the invention, although the invention is notlimited by these Examples. The instruments used in the Examples were asfollows.

[¹H-NMR]

Instruments: Varian NMR System 400 NB (400 MHz) JEOL-ECA700 (700 MHz)

Solvent used in measurement: DMSO-d6

Reference material: Tetramethylsilane (TMS) (δ=0.0 ppm)

[GPC]

Instrument: SCL-10Avp (Shimadzu Corporation), modified for GPC

Columns: Shodex KF-804L+KF-805L

Column temperature: 60° C.

Solvent: N-methyl-2-pyrrolidone (NMP) (1% LiCl)

Detector: UV (254 nm)

Calibration curve: polystyrene standard

[Ultraviolet/Visible Spectrophotometer]

Instrument: UV-3600 (Shimadzu Corporation)

[Ellipsometer]

Instrument: VASE multiple incident angle spectroscopic ellipsometer (JAWoollam Japan)

[Thermogravimetric/Differential Thermal Analyzer (TG-DTA)]

Instrument: TG-8120 (Rigaku Corporation)

Temperature rise rate: 10° C./min

Measurement temperatures: 25° C. to 750° C.

[Electron Microscope]

S-4800 electron microscope, from JEOL Ltd.

-   [1] Triazine Ring-Containing Polymer Synthesis

Working Example 1-1 Synthesis of Polymeric Compound [5]

Under nitrogen, 3,5-diaminobenzoic acid [2] (3.04 g, 0.02 mol),m-phenylenediamine [3] (1.08 g, 0.01 mol), 2,6-dimethylaniline [4] (1.21g, 0.01 mol) and 81.49 g of NMP were added to a 100 mL four-neck flaskand cooled to −10° C. on an acetone-dry ice bath. Next, a solution of2,4,6-trichloro-1,3,5-triazine [1] (9.22 g, 0.05 mol; Evonik Degussa)dissolved in 69.85 g of THF was added dropwise and the flask contentswere stirred for 1 hour. This reaction mixture was added dropwise over30 minutes to a reactor consisting of a 300 mL four-neck flask to whichhad been added 81.49 g of NMP and which was preheated to 85° C. on anoil bath. Following such addition, the system was stirred for 2 hours,effecting polymerization.

Next, 11.31 g (0.125 mol) of aniline was added and the flask contentswere stirred for 1 hour, bringing the reaction to completion. The systemwas cooled to room temperature in an ice bath, after which n-propylamine(6.21 g, 0.105 mol) was added dropwise and 1 hour of stirring wascarried out, thereby quenching the hydrochloric acid. The reactionmixture was then reprecipitated in deionized water (1,397 g). Theprecipitate was filtered, re-dissolved in THF (77.6 g), and stirred for1 hour. The supernatant was discarded, after which THF (25.87 g) wasadded to adjust the concentration and reprecipitation was carried out indeionized water (620.9 g). The resulting precipitate was filtered, thendried in a vacuum desiccator at 100° C. for 5 hours, giving 12.5 g ofthe target polymeric compound [5] (abbreviated below as “H-24X”). FIG. 1shows the measured ¹H-NMR spectrum for Polymeric Compound [5].

The polystyrene-equivalent weight-average molecular weight (Mw) ofH-24X, as measured by GPC, was 1,200, and the polydispersity Mw/Mn was1.32.

Upon weighing out 5.87 mg of Polymeric Compound [5] obtained in WorkingExample 1-1 onto a platinum pan and carrying out measurement by TG-DTAat a temperature rise rate of 15° C./min, the 5% weight loss temperaturewas 355.4° C.

The solutions obtained when the polymeric compound synthesized inWorking Example 1-1 was dissolved to concentrations of 10 wt %, 20 wt %and 30 wt % in THF, cyclohexanone (CHN), cyclopentane (CP) and propyleneglycol monomethyl ether (PGME), and when the powder was dissolved in alarge amount of a 1% aqueous solution of Na₂CO₃, were visually checkedfor the presence of insoluble matter and evaluated according to thefollowing criteria. The results are shown in Table 1.

Good: No insoluble matter

Fair: Slight, scattered amount of insoluble matter

NG: Sediment is present

TABLE 1 Working Example 1-1 THF 10 wt % good 20 wt % good 30 wt % goodCHN 10 wt % good 20 wt % good 30 wt % good CPN 10 wt % good 20 wt % good30 wt % good PGME 10 wt % good 20 wt % good 30 wt % fair 1% Na₂CO₃,aqueous good

As shown in Table 1, because the polymeric compound obtained in WorkingExample 1-1 is a polymeric compound having carboxyl group-containingarylene groups on the main chain, it has an excellent solubility invarious organic solvents and also in weakly alkaline aqueous solutions.

Working Example 1-2 Synthesis of Polymeric Compound [6]

Under nitrogen, 3,5-diaminobenzoic acid [2] (18.24 g, 0.12 mol; NipponJunryo Chemicals) was added to a 500 mL four-neck flask and dissolved in129.28 g of N,N-dimethylacetamide (DMAc), and the flask contents werecooled to not above 0° C. Next, 2,4,6-trichloro-1,3,5-triazine [1](18.44 g, 0.1 mol; Evonik Degussa) was added a little at a time so as tokeep the temperature within the system at 0° C. or below and the flaskcontents were stirred for 1 hour. This solution was added dropwise to a500 mL four-neck flask to which had been added 129.39 g of DMAc andwhich was preheated to 90° C. Following addition, the reaction waseffected at 90° C. for 2 hours, aniline (27.9 g, 0.3 mol; Tokyo ChemicalIndustry Co., Ltd.) was added dropwise and the system was stirred for 3hours. The temperature was then lowered to room temperature and 17.7 gof n-propylamine was added dropwise, stopping polymerization.

The resulting reaction mixture was added dropwise to 1,600 g ofdeionized water and re-precipitation was carried out. The resultingprecipitate was filtered and the filtered matter was re-dispersed in 262g of tetrahydrofuran, then re-precipitated in 1,596 g of deionizedwater. Next, the product obtained by filtration was dried at 120° C. for8 hours, giving 25.5 g of the target polymeric compound [6] (referred tobelow as “HB-TDCOOH”).

FIG. 2 shows the measured ¹H-NMR spectrum for Polymeric Compound [6].

Upon weighing out 5.200 mg of Polymeric Compound [6] obtained in WorkingExample 2-1 on a platinum pan and carrying out measurement by TG-DTA ata temperature rise rate of 15° C./min, the 5% weight loss temperaturewas 392° C.

-   [2] Film Production

Working Example 2-1

A film was obtained by dissolving Polymeric Compound [5] synthesized inWorking Example 1-1 in PGME to a concentration of 10 wt %, using a spincoater to spin coat the resulting solution onto a glass substrate, andcarrying out a 3-minute bake on a 120° C. hot plate.

Working Example 2-2

A 20 wt % polymer solution was prepared under nitrogen within a samplevial by dissolving 4.00 g of Polymeric Compound [6] obtained in WorkingExample 2-1 in 16.00 g of a mixed solvent ofPGME/n-propylamine/deionized water (72.25/12.25/15, by weight).

A film was obtained by dissolving this solution in PGME to aconcentration of 10 wt %, using a spin coater to spin coat the resultingsolution onto a glass substrate to a target film thickness of 700 nm andcarrying out a 1-minute bake on a 100° C. hot plate.

The refractive indices and film thicknesses of the films produced inWorking Examples 2-1 and 2-2 are shown in Table 2.

TABLE 2 Working Example 2-1 Working Example 2-2 Refractive index (at 550nm) 1.756 1.752 Film thickness (nm) 334 764

As shown in Table 2, the thin films produced from the polymeric compoundsynthesized in Working Example 1-1 had refractive indices higher than1.75.

-   [3] Preparation of Crosslinking Agent-Containing Composition, and    Patterning and Cured Film Production

Working Example 3-1

A patterning composition (6.36 g) having a solids content of 20 wt % wasprepared by adding the following to 0.6 g of Polymeric Compound [5]obtained in Working Example 1-1: 0.3 g of the polyacrylate DN-0075(Nippon Kayaku Co., Ltd.), 0.3 g of the polyacrylate A-GLY-20E(Shin-Nakamura Chemical Co., Ltd.), 0.06 g of the photoradical initiatorIrgacure OXE01 (BASF) and 5.04 g of PGME.

This composition was filtered with a 0.45 μm filter and coated onto aglass substrate using a spin coater, following which it was baked on ahot plate at 120° C. for 60 seconds, thereby forming a film. The filmwas irradiated through a photomask with ultraviolet light in a dose at365 nm of 100 mJ/cm² using a UV aligner (MA6, from Karl Suss). Next, thefilm was developed by 60 seconds of immersion in a 0.04 wt % aqueoussolution of potassium hydroxide at 23° C., and then rinsed withultrapure running water. Following development, a striped pattern withline/space dimensions of 60 μm/500 μm resolved without residues. Visualexamination under a sodium lamp was carried out, whereupon foreignmatter was not observed in the cured film that formed on the glasssubstrate. In addition, on carrying out electron microscopicexamination, foreign matter was not observed on the cured film.

The invention claimed is:
 1. A triazine ring-containing hyperbranchedpolymer comprising a recurring unit structure of formula (1) below

wherein R and R′ are each independently a hydrogen atom, an alkyl group,an alkoxy group, an aryl group or an aralkyl group; and Ar¹ is at leastone moiety selected from the group consisting of moieties of formulas(2) to (13)

wherein R¹ to R⁹² are each independently a hydrogen atom, a halogenatom, a carboxyl group, a sulfo group, an alkyl group of 1 to 10 carbonatoms which may have a branched structure, or an alkoxy group of 1 to 10carbon atoms which may have a branched structure; R⁹³ and R⁹⁴ are each ahydrogen atom or an alkyl group of 1 to 10 carbon atoms which may have abranched structure; W¹ and W² are each independently a single bond,CR⁹⁵R⁹⁶, wherein R⁹⁵ and R⁹⁶ are each independently a hydrogen atom oran alkyl group of 1 to 10 carbon atoms which may have a branchedstructure, and R⁹⁵ and R⁹⁶ may together form a ring, C═O, O, S, SO, SO₂or NR⁹⁷, R⁹⁷ being a hydrogen atom or an alkyl group of 1 to 10 carbonatoms which may have a branched structure; and X¹ and X² are eachindependently a single bond, an alkylene group of 1 to 10 carbon atomswhich may have a branched structure, or a group of formula (14)

wherein R⁹⁸ to R¹⁰¹ are each independently a hydrogen atom, a halogenatom, a carboxyl group, a sulfo group, an alkyl group of 1 to 10 carbonatoms which may have a branched structure, or an alkoxy group of 1 to 10carbon atoms which may have a branched structure; and Y¹ and Y² are eachindependently a single bond or an alkylene group of 1 to 10 carbon atomswhich may have a branched structure; with the proviso that formulas (2)to (13) all have at least one carboxyl group on one aromatic ringtherein, wherein the polymer has a least one triazine ring end, and atleast a portion of the triazine ring ends are capped with an arylaminogroup having an alkyl, alkoxy, aryl, or aralkyl group at at least oneortho position to the amino group thereon.
 2. The triazinering-containing polymer of claim 1, further comprising a recurring unitstructure of formula (1′) below

wherein R and R′ are each independently a hydrogen atom, an alkyl group,an alkoxy group, an aryl group or an aralkyl group; and Ar² is at leastone moiety selected from the group consisting of moieties of formulas(2′) to (13′)

wherein R^(1′) to R^(92′) are each independently a hydrogen atom, ahalogen atom, a sulfo group, an alkyl group of 1 to 10 carbon atomswhich may have a branched structure, or an alkoxy group of 1 to 10carbon atoms which may have a branched structure; R⁹³ and R⁹⁴ are each ahydrogen atom or an alkyl group of 1 to 10 carbon atoms which may have abranched structure; W¹ and W² are each independently a single bond,CR⁹⁵R⁹⁶, wherein R⁹⁵ R⁹⁵ and R⁹⁶ are each independently a hydrogen atomor an alkyl group of 1 to 10 carbon atoms which may have a branchedstructure, and R⁹⁵ and R⁹⁶ may together form a ring, C═O, O, S, SO, SO₂,or NR⁹⁷, R⁹⁷ being a hydrogen atom or an alkyl group of 1 to 10 carbonatoms which may have a branched structure; and X^(1′) and X^(2′) areeach independently a single bond, an alkylene group of 1 to 10 carbonatoms which may have a branched structure, or a group of formula (14′)

wherein R^(98′) to R^(101′) are each independently a hydrogen atom, ahalogen atom, a sulfo group, an alkyl group of 1 to 10 carbon atomswhich may have a branched structure, or an alkoxy group of 1 to 10carbon atoms which may have a branched structure; and Y¹ and Y² are eachindependently a single bond or an alkylene group of 1 to 10 carbon atomswhich may have a branched structure.
 3. The triazine ring-containingpolymer of claim 2, wherein Ar² has formula (17).


4. The triazine ring-containing polymer of claim 1, wherein Ar¹ hasformula (15).


5. The triazine ring-containing polymer of claim 4, wherein Ar¹ hasformula (16)


6. The triazine ring-containing polymer of claim 1, wherein thearylamino group has the alkyl, alkoxy, aryl or aralkyl group at bothortho positions to the amino group thereon.
 7. The triazinering-containing polymer of claim 6, wherein the arylamino group hasformula (18).


8. A triazine polymer-containing composition comprising the triazinering-containing polymer of claim 1 and an organic solvent.
 9. Thetriazine polymer-containing composition of claim 8 which furthercomprises a crosslinking agent.
 10. The triazine polymer-containingcomposition of claim 9, wherein the crosslinking agent is apoly(meth)acrylic compound.
 11. A cured film obtained by curing thetriazine polymer-containing composition of claim
 9. 12. A patternproduced from the triazine polymer-containing composition of claim 9.13. An electronic device comprising a substrate and the cured film ofclaim 11 formed on the substrate.
 14. An optical member comprising asubstrate and the cured film of claim 11 formed on the substrate.
 15. Anelectronic device comprising a substrate and the pattern of claim 12formed on the substrate.